The present invention relates to novel bis-1,2-naphthoquinone-2-diazide-sulfonic acid amides of secondary diamines. The present invention also relates to the use of bis-1,2-naphthoquinone-2-diazide-sulfonic acid amides as radiation-sensitive components in a radiation-sensitive mixture, and to radiation-sensitive copying materials prepared from such a mixture.
A large number of derivatives, especially aromatic esters, of 1,2-naphthoquinone-2-diazide-sulfonic acids are already known to be useful as light-sensitive components in positive-working copying materials. A number of light-sensitive naphthoquinone-diazides are described by Jaromir Kosar in LIGHT-SENSITIVE SYSTEMS (John Wiley & Sons/New York, 1965), at pages 343-51.
The continuing trend toward miniaturization in the manufacture of electronic components requires the production of increasingly smaller structures. An important step in the manufacture of such components is the imagewise exposure and subsequent development of light-sensitive films that are applied to the material which is to be structured. The wavelength of the light used for exposure is a factor limiting the resolution capacity of light-sensitive layers, and structures having smaller dimensions can be produced with light of shorter wavelength. The conventionally used materials, however, show good light sensitivity only in the visible or near UV range (365-450 nm), whereas they display only inadequate light sensitivity in the shorter-wavelength range (300-350 nm). The naphthoquinone-diazide derivatives used heretofore have unsuitable absorption properties in the so-called mid-UV (300-350 nm), i.e., the materials are only slightly bleached by exposure at 313 nm.
The effect of substituents on the absorption properties in this range of napthoquinone-diazides has already been investigated (see Grant Willson et al., "Design of a positive resist for projection lithography in the mid-UV," presented at The Sixth International Technical Conference on Photopolymers, November 1982, Ellenville/USA); it has been found that naphthoquinonediazide-4- and -5-alkylsulfonates have favorable absorption properties in the range from 300 to 350 nm. The mercury vapor lamps conventionally used in exposure apparatus have, in the wavelength range from 300 to 350 nm, two emission lines at 313 and 334 nm, so that exposure of suitable materials in this wavelength range is possible.
The disadvantage of inadequate light sensitivity on exposure in the mid-UV has already been recognized, and attempts made to overcome it by the use of bis-1,2-napthoquinone-2-dizide-sulfonic acid esters of aliphatic diols, as described in European patent application No. 0 085 761 (corresponding to U.S. Pat. No. 4,397,937). But only a very limited number of tricyclic diols have been disclosed so far and, in addition, their preparation is possible only with the use of 4-dimethylamino-pyridine as a very expensive catalyst. The latter drawback also applied to the aliphatic esters of naphthoquinone-diazide-sulfonic acids, mentioned in European patent application No. 0 147 596, U.S. Pat. No. 4,417,810, 11-29-83, the preparation of which esters is possible only with the use of 4-dimethylaminopyridine or 4-(1-pyrrolidino)-pyridine.
The instability of arylsulfonic acid alkyl esters, which are used as alkylating agents, for example, in the preparation of ethers (compare Houben-Weyl, METHODEN DER ORGANISCHEN CHEMIE [Methods of Organic Chemistry], Volume IX (4th ed. 1955) at pages 674 et seq. (G. Thieme Verlag, Stuttgart), is generally known in the literature.